System and method for cryogenic purification of a feed stream comprising hydrogen, methane, nitrogen and argon

ABSTRACT

A system and method for cryogenic purification of a hydrogen, nitrogen, methane and argon containing feed stream to produce a methane free, hydrogen and nitrogen containing synthesis gas and a methane rich fuel gas, as well as to recover an argon product stream, excess hydrogen, and excess nitrogen is provided. The disclosed system and method are particularly useful as an integrated cryogenic purifier in an ammonia synthesis process in an ammonia plant. The excess nitrogen is a nitrogen stream substantially free of methane and hydrogen that can be used in other parts of the plant, recovered as a gaseous nitrogen product and/or liquefied to produce a liquid nitrogen product.

TECHNICAL FIELD

The present invention relates to an integrated cryogenic purificationsystem and method for chemical plants, such as an ammonia plant. Moreparticularly the present invention relates to a system and method forcryogenic purification and recovery of argon, hydrogen, and nitrogenfrom a crude synthesis gas feed stream comprising hydrogen, nitrogen,methane and argon to recover argon, as well as excess hydrogen andnitrogen.

BACKGROUND

The availability of low cost natural gas has led to the restart andconstruction of numerous ammonia production facilities throughout NorthAmerica. Ammonia is typically produced through steam methane reforming.In the steam methane reforming process, air is used to auto-fire thereaction and to supply nitrogen for the ammonia synthesis reaction. Ingeneral, the steam methane reforming based process consists of primarysteam reforming, secondary ‘auto-thermal’ steam reforming followed by awater-gas shift reaction and carbon oxide removal processes to produce asynthesis gas. The synthesis gas is subsequently dried to produce a rawnitrogen-hydrogen process gas with small amounts of methane and inertswhich is then fed to an ammonia synthesis reaction. In many ammoniaproduction plants, the raw nitrogen-hydrogen process gas is oftensubjected to a number of purification or additional process steps priorto the ammonia synthesis reaction.

A commercially important part of the ammonia processing train often usedin ammonia plants is a cryogenic purification process known by thoseskilled in the art as the ‘Braun Purifier’. Since the secondary reformeris fed with an air flow having a nitrogen content that is larger thanthat required by the stoichiometry of the ammonia synthesis reaction,excess nitrogen, unconverted methane and inert gases must be removed orrejected from the raw nitrogen-hydrogen process gas prior to the ammoniasynthesis step. In order to reject the excess nitrogen, unconvertedmethane and inerts, the Braun-type cryogenic purification process isintroduced after the methanation reaction. The primary purpose of thisBraun-type cryogenic purification process is to generate an overheadammonia synthesis gas stream with a stoichiometric ratio of hydrogen tonitrogen (H2:N2) of about 3:1 and low levels of methane and inerts.

The cryogenic purification step of the Braun Purifier typically employsa single stage of refrigerated rectification. The overhead synthesis gasstream from the single stage of refrigerated rectification issubstantially free of unconverted methane and a substantial portion ofthe inerts, such as argon, are rejected into the fuel gas stream-bottomsliquid. In the Braun Purifier process, the feed gas stream is firstcooled and dehydrated. The feed gas stream is then partially cooled andexpanded to a lower pressure. The feed gas stream may be further cooledto near saturation and partially condensed and then directed to the baseof the single stage rectifier. The rectifier overhead is the resultingammonia synthesis gas that is processed for ammonia synthesis, whereasthe rectifier bottoms are partially vaporized by passage through therectifier condenser and warmed to ambient temperatures. This fuel/wastestream is typically directed back to the reformer and serves as fuel.See Bhakta, M., Grotz, B., Gosnell, J., Madhavan, S., “Techniques forIncrease Capacity and Efficiency of Ammonia Plants”, Ammonia TechnicalManual 1998, which provides additional details of this Braun Purifierprocess.

The waste gas from the Braun Purifier process step is predominantly amixture of hydrogen (6.3 mole %), nitrogen (76.3 mole %), methane (15.1mole %) and argon (2.3 mole %). The conventional argon recoveryprocesses from ammonia tail gas are typically integrated with thehydrogen recovery process downstream of the Braun purifier. Theconventional argon recovery processes are relatively complex andinvolves multiple columns, vaporizers, compressors, and heat exchangers,as described for example in W. H Isalski, “Separation of Gases” (1989)pages 84-88. Other relatively complex argon recovery systems and processare disclosed in U.S. Pat. Nos. 3,442,613; 5,775,128; 6,620,399;7,090,816; and 8,307,671. Similarly, systems and processes for therecovery of argon, hydrogen and nitrogen from the waste gas aredisclosed in U.S. Pat. Nos. 3,666,415; 3,675,434; 4,058,589; 4,077,780;4,524,056; 4,752,311 and United. States Patent Application PublicationNo. 2013/0039835; and 2016/0060130. While these waste gas processingsolutions adequately recover the argon, hydrogen and nitrogen, they doso at additional capital and operating costs.

What is needed therefore is an efficient and cost effective solution forrecovery of the hydrogen, methane, nitrogen, and argon that ispreferably integrated with the cryogenic purification of the synthesisgas.

SUMMARY OF THE INVENTION

The present invention may be characterized as a cryogenic purificationsystem configured for purifying a hydrogen, nitrogen, methane and argoncontaining feed stream, the purification system comprising: (i) asynthesis gas rectification column configured to receive the feed streamand produce a hydrogen and nitrogen enriched overhead vapor stream and amethane-rich condensed phase stream proximate the bottom of thesynthesis gas rectification column; (ii) a hydrogen stripping columnconfigured to receive the methane-rich condensed phase stream from thesynthesis gas rectification column, strip hydrogen from the methane-richcondensed phase stream and produce a hydrogen free methane bottom streamand a hydrogen enriched gaseous overhead; (iii) a condenser configuredto receive the hydrogen free methane bottom stream and a working fluidand to produce a vaporized or partially vaporized hydrogen freemethane-rich stream; and (iv) a heat exchanger configured to (a) warmthe hydrogen and nitrogen enriched overhead vapor stream via indirectheat exchange with the feed stream to produce a hydrogen and nitrogencontaining synthesis gas; and (b) to warm the vaporized or partiallyvaporized hydrogen free methane-rich stream via indirect heat exchangewith the feed stream to produce a methane fuel gas.

The present invention may be characterized as a cryogenic purificationsystem configured for purifying a hydrogen, nitrogen, methane and argoncontaining feed stream, the cryogenic purification system comprising:(i) a synthesis gas rectification column configured to receive thehydrogen, nitrogen, methane and argon containing feed stream and producea hydrogen and nitrogen enriched overhead vapor stream and amethane-rich condensed phase stream proximate the bottom of thesynthesis gas rectification column; (ii) a condenser-reboiler disposedwithin the synthesis gas rectification column configured to vaporize thehydrogen free methane bottom stream against a working fluid to produce avaporized or partially vaporized hydrogen free methane rich stream;(iii) a nitrogen rectification column configured to receive thevaporized or partially vaporized hydrogen free methane bottom stream anda liquid nitrogen reflux stream and produce a nitrogen containingoverhead vapor stream substantially free of methane, and a methaneenriched liquid bottom stream; (iv) a heat exchanger configured to (a)warm the hydrogen and nitrogen enriched overhead vapor stream viaindirect heat exchange with the hydrogen, nitrogen, methane and argoncontaining feed stream to produce a hydrogen and nitrogen containingsynthesis gas; (b) to warm the nitrogen containing overhead vapor streamsubstantially free of methane to produce a warm gaseous nitrogen stream,and (c) to warm the methane enriched liquid bottom stream to produce amethane fuel gas; and (v) a nitrogen recovery system configured toreceive the warm nitrogen containing stream and produce at least onenitrogen product.

In some of the preferred embodiments, the feed gas may be conditionedvia pre-purification of the feed stream, further compression orexpansion of the feed stream to a pressure that is preferably greaterthan or equal to about 300 psia, and/or cooling of the feed stream to atemperature near saturation, and warming of the feed stream. Thepre-purification of the feed stream may involve removing selectedimpurities or contaminants from the crude feed stream in an adsorptionbased pre-purifier or getter.

In embodiments that include hydrogen recovery, the present systems mayfurther include a second heat exchanger configured for cooling themethane-rich condensed phase stream to produce a cooled methane-richstream; and an expansion valve disposed downstream of the second heatexchanger and upstream of the hydrogen stripping column and configuredto expand the cooled methane-rich stream to a pressure less than orequal to about 100 psia. Such embodiments may also include a recyclecircuit configured to recycle the hydrogen rich gaseous overhead fromthe hydrogen stripping column back to the hydrogen, nitrogen, methaneand argon containing feed stream or the conditioned feed stream. Ahydrogen compressor may be disposed within the recycle circuit upstreamof the feed stream and configured to compress the hydrogen rich gaseousoverhead stream to a pressure greater than or equal to the pressure ofthe hydrogen, nitrogen, methane and argon containing feed stream or theconditioned feed stream. In such embodiments, the hydrogen enrichedgaseous overhead from the hydrogen stripping column is preferably warmedin the heat exchanger via indirect heat exchange with the hydrogen,nitrogen, methane and argon containing feed stream.

In embodiments that include nitrogen recovery, the present systemsinclude a nitrogen rectification column configured to receive thevaporized or partially vaporized hydrogen free methane-rich stream and anitrogen reflux stream and produce a nitrogen containing overhead vaporstream substantially free of methane and hydrogen, and a methaneenriched liquid bottom stream. The resulting methane enriched liquidbottom stream is preferably warmed in the heat exchanger via indirectheat exchange with the feed stream to produce the methane fuel gas whilethe nitrogen containing overhead vapor stream substantially free ofmethane and hydrogen is also warmed in the heat exchanger via indirectheat exchange with the feed stream to produce a warm nitrogen stream.The warmed nitrogen stream is then directed to a nitrogen recoverysystem, such as a liquefier, or purification system configured toproduce at least one nitrogen product, preferably a liquid nitrogenstream or a purified gaseous nitrogen stream.

In embodiments that include argon recovery, the present systems furthercomprises an argon rectification column configured to receive an argonenriched stream substantially free of methane from an intermediatelocation of the nitrogen rectification column and produce an argonbottoms liquid stream and a nitrogen enriched overhead stream. Thenitrogen enriched overhead stream is then returned to the nitrogenrectification column while the argon bottoms liquid stream is extractedfrom the argon rectification column as a crude argon product stream.

BRIEF DESCRIPTION OF THE DRAWINGS

While the specification concludes with claims specifically pointing outthe subject matter that Applicant regards as the invention, it isbelieved that the invention will be better understood when taken inconnection with the accompanying drawings in which;

FIG. 1 is a schematic representation of an embodiment of a cryogenicpurifier system and method in accordance with one aspect of the presentinvention;

FIG. 2 is a schematic representation of another embodiment of acryogenic purifier system and method with enhanced nitrogen recovery inaccordance with another aspect of the present invention;

FIG. 3 is a schematic representation of another embodiment of acryogenic purifier system and method with enhanced nitrogen recovery;

FIG. 4 is a schematic representation of yet another embodiment of acryogenic purifier system and method with enhanced nitrogen and argonrecovery in accordance with another aspect of the present invention; and

FIG. 5 is a schematic representation of an integrated nitrogen liquefiersuitable for use with the embodiments of the integrated cryogenicpurifier systems and methods depicted in FIGS. 1 through 4.

For sake of clarity, many of the reference numerals used in FIGS. 1-5are similar in nature such that the same reference numeral in one figurecorresponds to the same item, element or stream as in the other figures.

DETAILED DESCRIPTION

The following detailed description provides one or more illustrativeembodiments and associated methods for cryogenic purification of a feedstream comprising hydrogen, nitrogen, methane and argon into its majorconstituents. The various embodiments include: (i) a cryogenic purifiersystem with stripping of excess hydrogen and recycling of the strippedhydrogen to the feed stream so as to increase the synthesis gasproduction; (ii) a cryogenic purifier system with enhanced recovery ofnitrogen; (iii) a cryogenic purifier system with enhanced recovery ofnitrogen and argon; and (iv) a cryogenic purifier system with anintegrated nitrogen liquefier. Each of these embodiments will bedescribed in the paragraphs that follow.

Cryogenic Purifier with Recycled Hydrogen Stream

Turning now to FIG. 1, a schematic representation of an integratedcryogenic purification system 10 is shown. As seen therein, apre-purified feed stream 12 comprising hydrogen, nitrogen, methane andargon at a pressure greater than about 300 psia is cooled to atemperature near saturation in a primary heat exchanger 20. Theresulting conditioned feed stream 18 is directed to a synthesis gasrectification column 30 that is configured to produce a hydrogen andnitrogen enriched overhead vapor stream 34 and a methane-rich condensedphase stream 32 proximate the bottom of the synthesis gas rectificationcolumn 30. In ammonia plant applications that employ the cryogenicpurification system, the hydrogen and nitrogen enriched overhead vaporstream 34 would preferably have a hydrogen to nitrogen ratio of about3:1. Also, as discussed in more detail below, the pre-purified feedstream 12 may be combined with a compressed hydrogen recycle stream 14upstream of the heat exchanger 20 and the resulting high pressure mixedfeed stream 16 comprising hydrogen, nitrogen, methane and argon iscooled to near saturation.

The conditioning of the feed streams may further include additionalcompression, expansion, cooling, condensing and/or vaporizing stepsdepending upon the source of the feed streams. Likewise,pre-purification of the feed streams preferably includes removingselected contaminants from the feed stream in an adsorption basedpre-purifier (not shown). For example, in some applications residualcarbon oxide impurities at levels less than about 10.0 ppm or otherunwanted impurities and low boiling contaminants may accompany the crudefeed stream. In such circumstances, adsorbents, getters or otherpurification systems (not shown) can be employed to further remove suchimpurities and low boiling contaminants from the crude feed streams,which could be, for example, a crude synthesis gas from an ammoniaplant. Such pre-purification may be conducted while a portion of thecrude feed stream is in the liquid phase or predominately gas phase andeither upstream, downstream or in conjunction with the conditioning ofthe feed streams.

A portion of the methane rich condensed phase stream 32 from the bottomof the synthesis gas rectification column 30 is then extracted as stream35 and directed to a hydrogen stripping column 40 configured to striphydrogen from the methane rich condensed phase stream 35 and produce ahydrogen free methane bottom stream 42 and a hydrogen enriched gaseousoverhead 44.

In the illustrated embodiment, the portion of the methane rich condensedphase stream 35 is first subcooled in subcooler 37 via indirect heatexchange with a diverted first portion 46 of the hydrogen free methanebottom stream 42. The subcooled methane rich stream 38 is expanded orflashed to a lower pressure by expansion valve 39 to a pressure lessthan or equal to about 100 psia with the lower pressure methane richstream 41 introduced proximate the top of the hydrogen stripping column40. The warmed first portion 48 of the of the hydrogen free methanebottom stream is then reintroduced into the hydrogen stripping column40.

A second portion 45 of the hydrogen free methane bottom stream 42 isextracted from the hydrogen stripping column 40, expanded in valve 49and directed as stream 47 to a condenser-reboiler disposed within thesynthesis gas rectification column 30 where it is vaporized against aworking fluid such as a nitrogen rich liquid to produce a vaporized orpartially vaporized hydrogen free methane-rich stream 51. While thepresent Figures illustrate the vaporization of the hydrogen-free methanebottom stream occurring in a condenser-reboiler disposed within thesynthesis gas rectification column, it is also contemplated to employ aseparate, stand-alone vaporizer or perhaps integrate the vaporizationstep within other heat exchangers within the cryogenic purificationsystem 10. In the embodiment of FIG. 1, the partially vaporized hydrogenfree methane-rich stream 51 is directed to phase separator 70 where itis separated into a vapor phase stream 74 and a liquid phase stream 72to facilitate feed distribution into the heat exchanger, as optimaldistribution of a two phase stream directly into the heat exchanger isdifficult and often leads to poor heat exchanger performance. The vaporphase stream 74 and liquid phase stream 72 (collectively stream 76) arethen directed to heat exchanger 20 where the stream(s) are furtherwarmed via indirect heat exchange with the mixed feed stream 16 toproduce a methane containing fuel gas stream 24.

The hydrogen enriched gaseous overhead 44 from the hydrogen strippingcolumn 40 is recycled as stream 43 via valve 25 and warmed in the heatexchanger 20. The warmed hydrogen recycle stream 22 is preferablyrecompressed in compressor 15 and the compressed recycle stream 14 iscombined with the pre-purified feed stream 12. Alternatively, thehydrogen recycle stream may be cooled separately and introduced as aseparate stream into the base of the synthesis gas rectification column30. Further alternatives contemplate combining the hydrogen enrichedgaseous overhead 44 from the hydrogen stripping column 40 with otherfuel gas streams such as the partially vaporized hydrogen freemethane-rich stream 51 and further processed as described above toproduce the warmed fuel gas stream 24.

The hydrogen and nitrogen enriched overhead vapor stream 34 is takenfrom the synthesis gas rectification column 30 as a stream 36 anddirected to heat exchanger 20 where it is warmed via indirect heatexchange with the mixed feed stream 16 to produce the hydrogen andnitrogen containing synthesis gas stream 26. As indicated above, inapplications involving ammonia synthesis, the hydrogen to nitrogen ratioin the hydrogen and nitrogen enrich overhead vapor stream and thehydrogen and nitrogen containing synthesis gas stream is preferablyabout 3:1.

For purposes of adding refrigeration to the cryogenic purificationprocess, a cryogenic refrigeration stream 80 may be introduced into theprocess. The cryogenic stream 80 is preferably comprised of liquidnitrogen, but may also contain or comprise other cryogen refrigerants(e.g. CH₄, Ar, etc.). In lieu of the supplemental refrigeration stream,it is possible to produce the supplemental refrigeration using aturbine, however such optional use of a separate turbine to produce therequired refrigeration requires additional capital costs.

Cryogenic Purifier with Enhanced Nitrogen Recovery

Turning now to FIGS. 2 and 3, there is shown embodiments of a cryogenicpurifier system and method with enhanced recovery of nitrogen both withupstream hydrogen stripping (FIG. 2) and without upstream hydrogenstripping (FIG. 3).

The integrated cryogenic purification systems 10 shown in FIG. 2 andFIG. 3 include the pre-purified feed stream 12, compressed hydrogenrecycle stream 14, high pressure mixed feed stream 16, conditioned feedstream 18, synthesis gas rectification column 30, hydrogen and nitrogenenriched overhead vapor stream 34, methane-rich condensed phase stream32 as generally shown and described with reference to FIG. 1, and forsake of brevity will not be repeated here. Also, like the embodiment ofFIG. 1, the hydrogen and nitrogen enriched overhead vapor stream 34 ofFIGS. 2 and 3 are also taken from the synthesis gas rectification column30 as stream 36 and directed to heat exchanger 20 where it is warmed viaindirect heat exchange with the mixed feed stream 16 to produce thehydrogen and nitrogen containing synthesis gas stream 26. Preferably,the hydrogen to nitrogen ratio in the hydrogen and nitrogen enrichoverhead vapor stream and the hydrogen and nitrogen containing synthesisgas stream is about 3:1.

In addition, the embodiment shown in FIG. 2 also includes the methanerich stream 35, the hydrogen stripping column 40, the hydrogen freemethane bottom stream 42, the hydrogen enriched gaseous overhead 44, thesubcooler 37, the subcooled methane rich stream 38, the expanded methanerich stream 41 as well as the diverted first portion 46 of the hydrogenfree methane stream 42 and subsequently warmed first portion 48 of theof the hydrogen free methane stream that are extracted from andreintroduced into the hydrogen stripping column 40, respectively. Theseelements and features of the illustrated embodiment are similar to oridentical to the corresponding features shown and described withreference to the embodiment of FIG. 1.

In the embodiment of FIG. 2, the hydrogen enriched gaseous overhead 44from the hydrogen stripping column 40 is preferably recycled as stream43 via valve 25 and warmed in the heat exchanger 20. The warmed hydrogenrecycle stream 22 is then recompressed in compressor 15 and thecompressed recycle stream 14 is combined with the pre-purified feedstream 12 in a manner similar to that described above with reference toFIG. 1. Alternatively, the hydrogen enriched gaseous overhead 44 fromthe hydrogen stripping column 40 may be combined with other fuel gasstreams and further processed as described above to produce the warmedfuel gas stream 24.

The main difference between the embodiment shown in FIG. 1 and theembodiment shown in FIG. 2 relates to the enhanced recovery of nitrogen.As taught above with reference to FIG. 1, a second portion 45 of thehydrogen free methane bottom stream 42 is extracted and directed viavalve 49 as stream 47 to a condenser-reboiler disposed within thesynthesis gas rectification column 30 where it is partially vaporizedagainst the synthesis gas rectification column overhead to produce apartially vaporized hydrogen free methane-rich stream 51.

In the embodiment of FIG. 2, this partially vaporized hydrogen freemethane-rich stream 51, is directed to a nitrogen rectification column50 configured to produce a nitrogen containing overhead vapor stream 54substantially free of methane and hydrogen, and a methane enrichedliquid bottom stream 52. To facilitate the rectification within thenitrogen rectification column 50, a liquid nitrogen reflux stream 53 isalso introduced to the nitrogen rectification column 50. The liquidnitrogen stream 80 preferably comes from an integrated nitrogenliquefier (See FIG. 5) where a diverted portion 83 of the liquidnitrogen stream 80 is introduced via valve 85 as liquid nitrogen refluxstream 53 to the upper portion of the nitrogen rectification column 50.Alternatively, the liquid nitrogen stream 80 may be derived from aremote liquid nitrogen source such as a remote liquid storage tank orreservoir (not shown).

A key aspect or feature of the present embodiment that enables a largefraction of the nitrogen to be recovered is the use of a mechanicalliquid pump for the re-pressurization of the methane enriched liquidbottoms taken from the nitrogen rectifier. The nitrogen rectificationcolumn preferably operates at a pressure below the fuel gas headerpressure, for example, at a pressure of less than or equal to about 50psia, and more preferably at a pressure of less than or equal to about25 psia. Alternatively, the use of a compressor to re-compresses thewarmed (i.e. vaporized) methane back to the pressure of the fuel gasheader may be used in lieu of the mechanical liquid pump.

The nitrogen containing overhead vapor stream 56 is warmed in heatexchanger 20 and the warmed nitrogen containing vapor stream 28 isdirected to a nitrogen recovery system (not shown in FIGS. 2 and 3) toproduce at least one nitrogen product, such as a gaseous nitrogenproduct and/or a liquid nitrogen product. A portion of the methane richliquid bottom stream 52 is extracted from the nitrogen rectificationcolumn 50 as a methane rich stream 55 which is pumped to an appropriatepressure and warmed in the heat exchanger 20 to produce the methane fuelgas 24. Preferably, the pumped methane rich stream 55 together with theoptional hydrogen vapor stream 43 (shown in FIG. 2) and any supplementalrefrigeration stream 80 is directed to the phase separator 70 where itis separated into a vapor phase stream 74 and a liquid phase stream 72(collectively stream 76) and directed to heat exchanger 20 where it iswarmed via indirect heat exchange with the mixed feed stream 16 toproduce the methane containing fuel gas 24. The phase separator 70(shown in FIG. 2) is an optional item in that it may not be needed inembodiments of the present system that only direct methane liquid and/orliquid nitrogen to the heat exchanger (See FIG. 3). The main differencebetween the embodiment shown in FIG. 2 and the embodiment shown in FIG.3 relates to the hydrogen stripping column and the hydrogen recyclingcircuit. In the embodiment of FIG. 3, the hydrogen stripping column andhydrogen recycling circuit are absent such that the hydrogen containing,methane rich stream 35 extracted from the synthesis gas rectificationcolumn 30 is directed via valve 49 as stream 47 to a condenser-reboilerdisposed within the synthesis gas rectification column 30 where it ispartially vaporized. This partially vaporized hydrogen and nitrogencontaining methane-rich stream 51A is directed to a nitrogenrectification column 50 along with a liquid nitrogen reflux stream 53where it is separated to produce a nitrogen and hydrogen containingoverhead vapor stream 54 substantially free of methane, and a methaneenriched liquid bottom stream 52.

The nitrogen and hydrogen containing overhead vapor stream 56 is warmedin heat exchanger 20 and directed to a nitrogen and hydrogen recoverysystem (not shown) to either separate the nitrogen and hydrogen asseparate products or to reintroduce the N₂—H₂ mixture into the NH₃synthesis train. Similar to the embodiment of FIG. 2, a portion of themethane rich liquid bottom stream 52 is extracted from the nitrogenrectification column 50 as a methane rich stream 55 typically at apressure of between about 15 psia and 25 psia which is pumped to anappropriate pressure of preferably between about 30 psia to 40 psia orhigher pressures, and subsequently warmed in the heat exchanger 20 toproduce the methane fuel gas 24.

Cryogenic Purifier with Enhanced Nitrogen and Argon Recovery

Turning now to FIG. 4, there is shown another embodiment of a cryogenicpurifier system and method similar to that shown in FIG. 2 but withenhanced recovery of both nitrogen and argon.

In many regards, the embodiment shown in FIG. 4 is very similar to theembodiment shown in FIG. 2, described above. The key difference betweenthe embodiment shown in FIG. 4 and the embodiment shown in FIG. 2relates to the enhanced recovery of argon using an argon rectificationcolumn 60 operatively coupled to the nitrogen rectification column 50.Preferably, an argon enriched stream 67 is extracted from anintermediate location of the nitrogen rectification column 50 andpreferably at a location that is substantially free of methane, forexample at a location where the methane concentration is less than about1.0 part per million (ppm) and more preferably less than about 0.1 ppm.The extracted argon enriched stream 67 may be a liquid stream, a gaseousstream, or a two phase stream comprising a fraction of liquid argon anda fraction of gaseous argon.

The extracted argon enriched stream 67 is directed to an argonrectification column 60 preferably operating at a pressure of betweenabout 65 psia and 80 psia and configured to separate the argon enrichedstream and produce an argon bottoms liquid stream 62 and a nitrogenenriched overhead stream 66. The nitrogen enriched overhead stream 66 issubsequently returned to the nitrogen rectification column 50 at alocation preferably above the intermediate location where the argonenriched stream 67 is extracted. The argon rectification column 60further includes a condenser-reboiler 65 configured to reboil argonrectification column 60. A portion of the descending argon liquid withinthe column 60 is vaporized in condenser-reboiler 65 against a stream ofcondensing gaseous nitrogen the resulting liquid nitrogen stream 68 maythen be directed to the top of column 50. Although pressurized nitrogen,such as a compressed portion of nitrogen stream 56 after warming, is thepreferred fluid to supply the reboil duty for argon rectification column60 other fluids could also be employed. The resulting argon bottomsliquid stream 62 from argon rectification column 60 is removed and couldbe taken directly as a crude argon merchant product or transported to aseparate or an offsite argon refinement process, where it could later befurther purified into suitable high purity argon product.

The liquid nitrogen stream 68 is preferably combined with liquid refluxstream 83. A first diverted portion of the liquid nitrogen stream 80 isa nitrogen reflux stream 53 introduced into the nitrogen rectificationcolumn 50. Reflux for column 50 may also be supplemented with thecondensed nitrogen derived from condenser-reboiler 65. A second divertedportion of the liquid nitrogen stream 80 can optionally be diverted asstream 84 and used to supplement the refrigeration of the presentpurification process independent of the operation of the rectificationcolumn 50.

While the preferred embodiment of the cryogenic purification system andprocess with nitrogen and argon recovery is described with reference toFIG. 4, alternative embodiments are contemplated where the upper portionof nitrogen rectification column may be configured atop the argonrectification column. In this alternate configuration, the bottom halfof the nitrogen column might be a separate column or may even beconfigured as a divided wall column.

Cryogenic Purifier with an Integrated Nitrogen Liquefier

Turning now to FIG. 5, there is shown an integrated nitrogen liquefierarrangement 100 suitable for use in the cryogenic purifier systems 10 ofFIGS. 1-4. As seen therein, the incoming stream 28 is preferably thewarmed nitrogen containing vapor stream received from theabove-described cryogenic purifier system 10 and compressed in amulti-stage compressor arrangement (shown in FIG. 5 as compressor stages102, 104). The compressed nitrogen stream 105 is optionally furthercompressed in a turbine loaded booster compressor 106.

A first portion 107 of the further compressed nitrogen vapor stream isdiverted from the booster compressor 106 to a refrigeration circuitwhere the first portion 107 is cooled via indirect heat exchange ineconomizer 115 with a refrigerant stream 118. The warmed refrigerantstream 116 is routed back to a chiller 117 where it is cooled andrecycled back to the economizer 115 in a generally closed loop fashion.The diverted and cooled first portion 108 of the further compressednitrogen stream is then expanded in turboexpander 130 with the resultantexhaust stream 109 directed to the heat exchanger 120 to supplysupplemental refrigeration to the integrated nitrogen liquefierarrangement and subsequently returned as warmed exhaust stream 121 to anintermediate stage of the multi-stage compressor arrangement 102/104, aspreferably shown in FIG. 5.

A second portion 111 of the further compressed nitrogen stream isdirected to the heat exchanger 120. Part of the second portion 111 ofthe further compressed nitrogen stream is only partially cooled in theheat exchanger 120 and diverted as stream 112 to the turbine 110 thatdrives the turbine loaded booster compressor. The remaining part of thesecond portion 111 of the further compressed nitrogen stream is fullycooled in the heat exchanger 120, valve expanded in expansion valve 125to form a second liquid or partially liquid nitrogen stream 126.

The resulting expanded nitrogen stream 114 is optionally directed to acondenser-reboiler 130 to condense or partially condense nitrogen stream114 to form a first liquid or partially liquid nitrogen stream 124. Theobjective of the condenser-reboiler 130 is optionally supply the reboilstream necessary to operate argon stripping column 60 (See FIG. 4). Inthis regard, condenser-reboiler 130 is the same as reboiler 65 of FIG.4. Alternatively, the reboil stream can be extracted from feed gascompressor 102 and directed in a separate pass into the reboiler 65 ofFIG. 4.

The liquid or partially liquid nitrogen streams 124, 126 are preferablymixed and directed as a combined stream to a first phase separator 140configured to produce a liquid nitrogen stream 142 and a cold gaseousnitrogen stream 144. The cold gaseous nitrogen stream 144 is sent to theheat exchanger 120 to recover some refrigeration and the resultingwarmed stream 123 is preferably mixed with the warmed exhaust stream 121and recycled back to an intermediate stage of the multi-stage compressorarrangement 102/104. Recycling of the warmed exhaust stream 121 and/orthe warmed stream 123 may be to an intermediate stage of the multi-stagecompressor arrangement 102/104 (shown in FIG. 5) or perhaps to alocation upstream or downstream of the multi-stage compressorarrangement 102/104 will depend on the pressures of the warmed exhauststream 121 and warmed stream 123.

The liquid nitrogen stream 142 extracted from the first phase separator140 is valve expanded in expansion valve 145 and directed to a secondphase separator 150 configured to produce a liquid nitrogen productstream 152 and a cold gaseous nitrogen stream 154 that may be warmed andrecycled back to incoming stream 28 after some or all of itsrefrigeration is recovered in heat exchanger 120. A stream of coldnitrogen vapor 155 may further represent an additional integration pointbetween the liquefier 100 and the cryogenic purification system 10. Ifthe argon and hydrogen has been previously recovered in the cryogenicpurification system 10, the liquid nitrogen product stream 152 and thegaseous nitrogen stream 154 will be purified. On the other hand, if theargon and/or hydrogen has not been previously recovered in the cryogenicpurification system 10, the liquid nitrogen product stream 152 and thegaseous nitrogen stream 154 may contain measurable levels of argonand/or hydrogen which can and should be recovered within theliquefaction arrangement 100 or in a separate upstream or downstreamrecovery process.

With respect to the above-described integrated nitrogen liquefierarrangement 100, it is also possible to incorporate multiple stages ofcompression and/or use multiple compressors arranged in parallel forpurposes of accommodating multiple return pressures of the recycledstreams. In addition, the turbo-expanded refrigerant stream 109 may bedirected to an intermediate location of the heat exchanger 120 (e.g.with respect to temperature) as the turbine discharge or exhaust doesnot have to be near saturation. The shaft work of expansion from turbine135 and/or turbine 110 can be directed to various compressors in otherprocess streams within the integrated cryogenic purification system 10or, as shown with respect to turbine 110 may be used to “self-boost” theexpansion stream. Alternatively, the shaft work of expansion fromturbine 135 and/or turbine 110 may also be loaded to a generator.

INDUSTRIAL APPLICABILITY

As integrated with an ammonia synthesis process in an ammonia productionplant, the present cryogenic purifier system and method takes a crudefeed stream comprising hydrogen, nitrogen, methane and argon andproduces the following product streams: (i) a hydrogen-nitrogensynthesis gas stream that may be recycled back to the ammonia plantsynthesis section, and more particularly the ammonia synthesis gasstream upstream of the compressor or of the ammonia plant; (ii) a highmethane content fuel gas that may be recycled back to the ammoniaproduction plant and preferably to the steam reforming section of theammonia plant, and more specifically to the furnace by which the primaryreformer is fired; (iii) a liquid argon product stream; and (iv) asubstantially pure nitrogen gaseous stream which may be recycled back tothe ammonia plant, taken as a gaseous nitrogen product, or morepreferably directed to a nitrogen recovery system, such as the liquefieras described above, to produce liquid and gaseous nitrogen products. Theoperating costs associated with the present integrated cryogenicpurifier system and method are substantially lower that a Braun Purifiersystem or other conventional cryogenic purification systems.

While the present invention has been described with reference to one ormore preferred embodiments and operating methods associated therewith,it should be understood that numerous additions, changes and omissionsto the disclosed system and method can be made without departing fromthe spirit and scope of the present invention as set forth in theappended claims.

What is claimed is:
 1. A cryogenic purification system configured forpurifying a hydrogen, nitrogen, methane and argon containing feedstream, the system comprising: a synthesis gas rectification columnconfigured to receive the feed stream and produce a hydrogen andnitrogen enriched overhead vapor stream and a methane-rich condensedphase stream at the bottom of the synthesis gas rectification column; ahydrogen stripping column configured to receive the methane-richcondensed phase stream from the synthesis gas rectification column,strip hydrogen from the methane-rich condensed phase stream and producea hydrogen free methane bottom stream and a hydrogen enriched gaseousoverhead; a condenser configured to receive the hydrogen free methanebottom stream and a working fluid and to vaporize the hydrogen freemethane stream to produce a vaporized hydrogen free methane-rich streamor a partially vaporized hydrogen free methane-rich stream; and a heatexchanger configured to (a) warm the hydrogen and nitrogen enrichedoverhead vapor stream via indirect heat exchange with the feed stream toproduce a hydrogen and nitrogen containing synthesis gas; and (b) towarm the vaporized hydrogen free methane-rich stream or the partiallyvaporized hydrogen free methane-rich stream via indirect heat exchangewith the feed stream to produce a methane fuel gas.
 2. The system ofclaim 1, further comprising a compressor disposed upstream of thesynthesis gas rectification column and configured to compress thehydrogen, nitrogen, methane and argon containing feed stream to apressure greater than about 300 psia.
 3. The system of claim 1, furthercomprising an adsorption based pre-purifier disposed upstream of thesynthesis gas rectification column and configured to remove selectedcontaminants from the hydrogen, nitrogen, methane and argon containingfeed stream.
 4. The system of claim 1, wherein the hydrogen to nitrogenratio in the hydrogen and nitrogen containing synthesis gas is about3:1.
 5. The system of claim 1, further comprising: a second heatexchanger configured for cooling the methane-rich condensed phasestream; and an expansion valve disposed downstream of the second heatexchanger and upstream of the hydrogen stripping column and configuredto expand the methane-rich stream to a pressure less than or equal toabout 100 psia; wherein hydrogen is stripped from the expandedmethane-rich stream within the hydrogen stripping column to produce thehydrogen free methane bottom stream and the hydrogen enriched gaseousoverhead.
 6. The system of claim 1, further comprising a recycle circuitconfigured to recycle the hydrogen rich gaseous overhead from thehydrogen stripping column back to the hydrogen, nitrogen, methane andargon containing feed stream.
 7. The system of claim 6, furthercomprising a hydrogen compressor disposed within the recycle circuitupstream of the feed stream and configured to compress the hydrogen richgaseous overhead stream to a pressure greater than or equal to thepressure of the hydrogen, nitrogen, methane and argon containing feedstream.
 8. The system of claim 7, wherein the hydrogen enriched gaseousoverhead from the hydrogen stripping column is warmed in the heatexchanger via indirect heat exchange with the hydrogen, nitrogen,methane and argon containing feed stream.
 9. A cryogenic purificationsystem configured for purifying a hydrogen, nitrogen, methane and argoncontaining feed stream, the system comprising: a synthesis gasrectification column configured to receive the feed stream and produce ahydrogen and nitrogen enriched overhead vapor stream and a methane-richcondensed phase stream at the bottom of the synthesis gas rectificationcolumn; a hydrogen stripping column configured to receive themethane-rich condensed phase stream from the synthesis gas rectificationcolumn, strip hydrogen from the methane-rich condensed phase stream andproduce a hydrogen free methane bottom stream and a hydrogen enrichedgaseous overhead; a condenser configured to receive the hydrogen freemethane bottom stream and a working fluid and to vaporize the hydrogenfree methane stream to produce a vaporized hydrogen free methane-richstream or a partially vaporized hydrogen free methane-rich stream; anitrogen rectification column configured to receive the vaporizedhydrogen free methane-rich stream or the partially vaporized hydrogenfree methane-rich stream and a nitrogen reflux stream and produce anitrogen containing overhead vapor stream substantially free of methaneand hydrogen, and a methane enriched liquid bottom stream; a heatexchanger configured to (a) warm the nitrogen containing overhead vaporstream substantially free of methane and hydrogen via indirect heatexchange with the feed stream to produce a warm nitrogen stream, and (b)warm the methane enriched liquid bottom stream via indirect heatexchange with the feed stream to produce a methane fuel gas.
 10. Thesystem of claim 9, further comprising a nitrogen recovery systemconfigured to receive the warm nitrogen stream and produce at least onenitrogen product.
 11. The system of claim 10, wherein the nitrogenrecovery system is a purification system configured to receive the warmnitrogen stream and produce the at least one nitrogen product, whereinthe at least one nitrogen product is a purified gaseous nitrogenproduct.
 12. The system of claim 10, wherein the nitrogen recoverysystem is a liquefier configured to receive the warm nitrogen stream andproduce the at least one nitrogen product, wherein the at least onenitrogen product is a liquid nitrogen product.
 13. The system of claim12, further comprising an integration circuit disposed between thenitrogen recovery system and the nitrogen rectification column, andwherein a portion of the liquid nitrogen product is used as the nitrogenreflux stream for the nitrogen rectification column.
 14. The system ofclaim 9, further comprising an argon rectification column configured toreceive an argon enriched stream substantially free of methane from anintermediate location of the nitrogen rectification column and producean argon bottoms liquid stream and a nitrogen enriched overhead stream;wherein the nitrogen enriched overhead stream is returned to thenitrogen rectification column; and wherein the argon bottoms liquidstream is extracted from the argon rectification column as a crude argonproduct stream.
 15. A cryogenic purification system configured forpurifying a hydrogen, nitrogen, methane and argon containing feedstream, the system comprising: a synthesis gas rectification columnconfigured to receive the hydrogen, nitrogen, methane and argoncontaining feed stream and produce a hydrogen and nitrogen enrichedoverhead vapor stream and a methane-rich condensed phase stream at thebottom of the synthesis gas rectification column; a condenser-reboilerdisposed within the synthesis gas rectification column configured tovaporize the hydrogen free methane bottom stream against a working fluidto produce a vaporized hydrogen free methane-rich stream or a partiallyvaporized hydrogen free methane-rich stream; a nitrogen rectificationcolumn configured to receive the vaporized hydrogen free methane-richstream or the partially vaporized hydrogen free methane-rich stream anda nitrogen reflux stream and produce a nitrogen containing overheadvapor stream substantially free of methane, and a methane enrichedliquid bottom stream; a heat exchanger configured to (a) warm thehydrogen and nitrogen enriched overhead vapor stream via indirect heatexchange with the hydrogen, nitrogen, methane and argon containing feedstream to produce a hydrogen and nitrogen containing synthesis gas; (b)warm the nitrogen containing overhead vapor stream substantially free ofmethane to produce a warm gaseous nitrogen stream, and (c) warm themethane enriched liquid bottom stream to produce a methane fuel gas; anda nitrogen recovery system configured to receive the warm nitrogencontaining stream and produce at least one nitrogen product.
 16. Thesystem of claim 15, further comprising a compressor disposed upstream ofthe synthesis gas rectification column and configured to compress thehydrogen, nitrogen, methane and argon containing feed stream to pressuregreater than about 300 psia.
 17. The system of claim 15, furthercomprising an adsorption based pre-purifier disposed upstream of thesynthesis gas rectification column and configured to remove selectedcontaminants from the hydrogen, nitrogen, methane and argon containingfeed stream feed to produce a conditioned feed stream.
 18. The system ofclaim 15, wherein the hydrogen to nitrogen ratio in the hydrogen andnitrogen containing synthesis gas is about 3:1.
 19. The system of claim15, wherein the nitrogen rectification column operates at a pressureless than or equal to about 50 psia.
 20. The system of claim 19, whereinthe nitrogen rectification column operates at a pressure less than orequal to about 25 psia.
 21. The system of claim 19, further comprising apump or compressor configured to pressurize the methane enriched streamto a pressure greater than the pressure of the nitrogen rectificationcolumn or greater than the pressure of a fuel gas header associated withthe cryogenic purification system.
 22. The system of claim 15, whereinthe warm gaseous nitrogen stream is free of hydrogen and the nitrogenrecovery system is a purification system configured to receive the warmnitrogen stream and produce the at least one nitrogen product andwherein the at least one nitrogen product is a gaseous nitrogen productsubstantially free of hydrogen.
 23. The system of claim 15, wherein thewarm gaseous nitrogen stream is free of hydrogen and the nitrogenrecovery system is a purification system configured to receive the warmnitrogen stream and produce the at least one nitrogen product andwherein the at least one nitrogen product is a purified gaseous nitrogenproduct.
 24. The system of claim 15, wherein the nitrogen recoverysystem is a liquefier configured to receive the warm nitrogen stream andproduce the at least one nitrogen product and wherein the at least onenitrogen product is a liquid nitrogen product.
 25. The system of claim24, further comprising an integration circuit disposed between thenitrogen recovery system and the nitrogen rectification column, andwherein a portion of the liquid nitrogen product is used as the refluxstream to the nitrogen rectification column.
 26. The system of claim 15,further comprising a hydrogen stripping column configured to receive themethane-rich condensed phase stream from the synthesis gas rectificationcolumn, strip hydrogen from the methane-rich condensed phase stream andproduce a hydrogen free methane bottom stream and a hydrogen enrichedgaseous overhead.
 27. The system of claim 26 further comprising: asecond heat exchanger disposed upstream of the hydrogen stripping columnconfigured for cooling the methane-rich condensed phase stream; and anexpansion valve disposed downstream of the second heat exchanger andupstream of the hydrogen stripping column and configured to expand themethane-rich stream to a pressure less than or equal to about 100 psia.28. The system of claim 26, further comprising a recycle circuitconfigured to recycle the hydrogen rich gaseous overhead from thehydrogen stripping column back to the hydrogen, nitrogen, methane andargon containing feed stream.
 29. The system of claim 26, furthercomprising a hydrogen compressor disposed within the recycle circuitupstream of the hydrogen, nitrogen, methane and argon containing feedstream and configured to compress the hydrogen rich gaseous overheadstream to a pressure greater than or equal to the pressure of thehydrogen, nitrogen, methane and argon containing feed stream.
 30. Thesystem of claim 28, wherein the hydrogen rich gaseous overhead streamfrom the hydrogen stripping column is warmed in the heat exchanger viaindirect heat exchange with the hydrogen, nitrogen, methane and argoncontaining feed stream.
 31. The system of claim 15, further comprisingan argon rectification column configured to receive an argon enrichedstream substantially free of methane from an intermediate location ofthe nitrogen rectification column and produce an argon bottoms liquidstream and a nitrogen enriched overhead stream; wherein the nitrogenenriched overhead stream is returned to the nitrogen rectificationcolumn; and wherein the argon bottoms liquid stream is extracted fromthe argon rectification column as a crude argon product stream.